Aquatic Geochemistry

, Volume 17, Issue 4–5, pp 583–601 | Cite as

Sulfide Oxidation across Diffuse Flow Zones of Hydrothermal Vents

  • Amy Gartman
  • Mustafa Yücel
  • Andrew S. Madison
  • David W. Chu
  • Shufen Ma
  • Christopher P. Janzen
  • Erin L. Becker
  • Roxanne A. Beinart
  • Peter R. Girguis
  • George W. LutherIII
Original Paper


The sulfide (H2S/HS) that is emitted from hydrothermal vents begins to oxidize abiotically with oxygen upon contact with ambient bottom water, but the reaction kinetics are slow. Here, using in situ voltammetry, we report detection of the intermediate sulfur oxidation products polysulfides [\( {\text{S}}_{\text{x}}^{2 - } \)] and thiosulfate [\( {\text{S}}_{ 2} {\text{O}}_{ 3}^{ 2- } \)], along with contextual data on sulfide, oxygen, and temperature. At Lau Basin in 2006, thiosulfate was identified in less than one percent of approximately 10,500 scans and no polysulfides were detected. Only five percent of 11,000 voltammetric scans taken at four vent sites at Lau Basin in May 2009 show either thiosulfate or polysulfides. These in situ data indicate that abiotic sulfide oxidation does not readily occur as H2S contacts oxic bottom waters. Calculated abiotic potential sulfide oxidation rates are <10−3 μM/min and are consistent with slow oxidation and the observed lack of sulfur oxidation intermediates. It is known that the thermodynamics for the first electron transfer step for sulfide and oxygen during sulfide oxidation in these systems are unfavorable, and that the kinetics for two electron transfers are not rapid. Here, we suggest that different metal catalyzed and/or biotic reaction pathways can readily produce sulfur oxidation intermediates. Via shipboard high-pressure incubation experiments, we show that snails with chemosynthetic endosymbionts do release polysulfides and may be responsible for our field observations of polysulfides.


Sulfide oxidation Kinetics Hydrothermal vents Diffuse flow Lau Basin In situ chemistry 



This paper is submitted in the memory and honor of John W. Morse who made significant contributions to geochemistry and oceanography including the founding of Aquatic Geochemistry (Mackenzie et al. 2010). This work was supported by grants from the US National Science Foundation (OCE-0732439 to GWL, OCE-0732369 to PRG, OCE-0732333 to Charles R. Fisher), via the Ridge 2000 program. None of this work would have been possible without the expertise and patience of the ROV JASON II and the R/V Melville crews in 2006, and the ROV JASON II, and the R/V Thomas G. Thompson crews in 2009. We thank Arunima Sen for her assistance with the substrate data. Special thanks to Dr. Charles R. Fisher for his skills as chief scientist and for facilitating data collection.


  1. Arp AJ, Menon JG, Julian D (1995) Multiple mechanisms provide tolerance to environmental sulfide in Urechis caupo. Am Zool 35:132–144Google Scholar
  2. Batina N, Cigenecki I, Cosovic B (1992) Determination of elemental sulphur, sulphide and their mixtures in electrolyte solutions by a.c. voltammetry. Anal Chim Acta 267:157–164CrossRefGoogle Scholar
  3. Bouchet P, Warén A (1991) Ifremeria nautilei, a new gastropod from hydrothermal vents, probably associated with symbiotic bacteria. C. R. ACAD. SCI. PARIS, SER. III 312(10):495–501Google Scholar
  4. Brendel, PJ, Luther GW III (1995) Development of a gold amalgam voltammetry microelectrode for the determination of dissolved Fe, Mn, O2, and S(-II) in porewaters of marine and freshwater sediments. Environ Sci Technol 29:751–761Google Scholar
  5. Chadwell SJ, Rickard D, Luther GW III (2001) Electrochemical evidence for metal polysulfide complexes: tetrasulfide (S4 2−) reactions with Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+. Electroanalysis 13:21–29CrossRefGoogle Scholar
  6. Chen KY, Gupta SK (1973) Formation of polysulfides in aqueous solution. Environ Lett 4(3):187–200CrossRefGoogle Scholar
  7. Chen KY, Morris JC (1972) Kinetics of Oxidation of Aqueous Sulfide by O2. Environ Sci Technol 6:529–537CrossRefGoogle Scholar
  8. Ciglenečki I, Ćosović B (1997) Electrochemical determination of thiosulphate in seawater in the presence of elemental sulphur and sulphide. Electroanalysis 9(10):1–7Google Scholar
  9. Cline JD (1969) Spectrophotometric determination of hydrogen sulfide in natural waters. Limnol Oceanogr 14:454–458CrossRefGoogle Scholar
  10. dos Santos Afonso M, Stumm W (1992) Reductive dissolution of Iron(III) (Hydr)oxides by hydrogen sulfide. Langmuir 8:1671–1675CrossRefGoogle Scholar
  11. Girguis PR, Childress JJ (2006) Metabolite uptake, stoichiometry and chemoautotrophic function of the hydrothermal vent tubeworm Riftia pachyptila: Responses to environmental variations in substrate concentrations and temperature. J Exp Biol 209(18):3516–3528CrossRefGoogle Scholar
  12. Gru C, Sarradin PM, Legoff H, Narcon S, Caprais JC, Lallier FH (1998) Determination of reduced sulfur compounds by high-performance liquid chromatography in hydrothermal seawater and body fluids from Riftia pachyptila. Analyst 123:1289–1293CrossRefGoogle Scholar
  13. Gun J, Goifman A, Shkrob I, Kamyshny A, Ginzburg B, Hadas O, Dor I, Modstov AD, Lev O (2000) Formation of Polysulfides in an oxygen rich freshwater lake and their role in the production of volatile sulfur compounds in aquatic systems. Environ Sci Technol 34:4741–4746CrossRefGoogle Scholar
  14. Hannington MD, Jonasson IR, Herzig PM, Petersen S (1995) Physical and chemical processes of seafloor mineralization at mid-ocean ridges, pp 115–157. In: Humphris SE, Zierenberg RA, Mullineaux LS, Thomson RE (eds) Seafloor hydrothermal systems: physical, chemical, biological, and geological interactions. Geophysical monograph 91. American Geophysical Union, Washington, DCGoogle Scholar
  15. Hayes MK, Taylor GT, Astor Y, Scranton MI (2006) Vertical distributions of thiosulfate and sulfite in the Caraico Basin. Limnol Oceanogr 51(1):280–287Google Scholar
  16. Henry MS, Childress JJ, Figueroa D (2008) Metabolic rates and thermal tolerances of chemoautotrophic symbioses from Lau Basin hydrothermal vents and their implications for species distributions, Deep Sea Research Part I: Oceanographic Research Papers 55(5):679–695Google Scholar
  17. Hoffmann MR (1977) Kinetics and mechanism of oxidation of hydrogen sulfide by hydrogen peroxide in acidic solution. Environ Sci Technol 11:61–66Google Scholar
  18. Jannasch HW, Wirsen CO (1979) Chemosynnthetic primary production at East Pacific Sea Floor spreading centers. Bioscience 29:592–598CrossRefGoogle Scholar
  19. Kamyshny A Jr, Ferdelman TG (2010) Dynamics of zero- valent sulfur species including polysulfides at seep sites on intertidal sand flats (Wadden Sea, North Sea). Mar Chem 121:17–26CrossRefGoogle Scholar
  20. Kleinjan WE, de Keizer A, Janssen AJH (2005) Kinetics of the chemical oxidation of polysulfide anions in aqueous solution. Water Res 39:4093–4100CrossRefGoogle Scholar
  21. Le Bris N, Sarradin PM, Caprais JC (2003) Contrasted sulphide chemistries in the environment of 13oN EPR vent fauna. Deep-Sea Res I 50:737–747CrossRefGoogle Scholar
  22. Le Bris N, Rodier P, Sarradin PM, Le Gall C (2006) Is temperature a good proxy for sulfide in hydrothermal vent habitats? Cah Biol Mar 47:465–470Google Scholar
  23. Luther GW III (2010) The role of one- and two-electron transfer reactions in forming thermodynamically unstable intermediates as barriers in multi- electron redox reactions. Aquat Geochem 16:395–420CrossRefGoogle Scholar
  24. Luther GW III, Bono A, Taillefert M, Cary SC (2002) A continuous flow electrochemical cell for analysis of chemical species and ions at high pressure: laboratory, shipboard and hydrothermal vent results. In: Taillefert M, Rozan T (eds) Environmental electrochemistry: analyses of trace element biogeochemistry. American Chemical Society Symposium Series; American Chemical Society, Washington, D. C., Chap 4, vol 811, pp 54–73Google Scholar
  25. Luther GW III, Giblin AE, Varsolona R (1985) Polarographic analysis of sulfur species in marine porewaters. Limnol Oceanogr 30(4):727–736CrossRefGoogle Scholar
  26. Luther GW III, Brendel PJ, Lewis BL, Sundby B, Lefrançois L, Silverberg N, Nuzzio DB (1998) Simultaneous measurement of O2, Mn, Fe, I, and S(-II) in marine pore waters with a solid-state voltammetric microelectrode. Limnol Oceanogr 43(2):325–333CrossRefGoogle Scholar
  27. Luther GW III, Rozan TF, Taillefert M, Nuzzio DB, Di Meo C, Shank TM, Lutz RA, Cary SC (2001a) Chemical speciation drives hydrothermal vent ecology. Nature 410:813–816CrossRefGoogle Scholar
  28. Luther GW III, Glazer BT, Hohmann L, Popp JI, Taillefert M, Rozan TF, Brendel PJ, Theberge SM, Nuzzio DB (2001b) Sulfur speciation monitored in situ with solid state gold amalgam voltammetric microelectrodes: polysulfides as a special case in sediments, microbial mats and hydrothermal vent waters. J Environ Monit 3:61–66CrossRefGoogle Scholar
  29. Luther GW III, Glazer BT, Ma S, Trouwborst RE, Moore TS, Metzger E, Kraiya C, Waite TJ, Druschel G, Sundby B, Taillefert M, Nuzzio DB, Shank TM, Lewis BL, Brendel PJ (2008) Use of voltammetric solid-state (micro)electrodes for studying biogeochemical processes: Laboratory measurements to real time measurements with an in situ electrochemical analyzer (ISEA). Mar Chem 108:221–235CrossRefGoogle Scholar
  30. Luther GW, Findlay AJ, MacDonald DJ, Owings SM, Hanson TE, Beinart RA, Girguis PR (2011) Thermodynamics and Kinetics of sulfide oxidation by oxygen: a look at inorganically controlled reactions and biologically mediated processes in the environment. Front Microbiol Physiol 62:1–9Google Scholar
  31. Mackenzie FT, Mucci A, Luther GW III (2010) In Memoriam: John W. Morse (1946–2009) Texas A&M University. Aquat Geochem 16:219–221CrossRefGoogle Scholar
  32. Maloy JT (1985) Nitrogen chemistry. In: Bard AJ, Parsons R, Jordan J (eds) Standard potentials in aqueous solution, 1st edn. M. Dekker, New York, pp 127–139Google Scholar
  33. Martinez F, Taylor B, Baker ET, Resing JA, Walker SL (2006) Opposing trends in crustal thickness and spreading rate along the back-arc Eastern Lau Spreading Center: implications for controls on ridge morphology, faulting, and hydrothermal activity. Earth Planet Sci lett 245:655–672CrossRefGoogle Scholar
  34. Mickel TJ, Childress JJ (1982) Effects of pressure and temperature on the EKG and heart rate of the hydrothermal vent crab Bythograea thermydron (Brachyura). Biol Bull 162:70–82CrossRefGoogle Scholar
  35. Millero FJ (1986) The thermodynamics and kinetics of the hydrogen sulfide system in natural waters. Mar Chem 18:121–147CrossRefGoogle Scholar
  36. Millero FJ, Hubinger S, Fernandez M, Garnett S (1987) Oxidation of H2S in seawater as a function of temperature, pH, and ionic strength. Environ Sci Technol 21:439–443CrossRefGoogle Scholar
  37. Moore TS, Shank TM, Nuzzio DB, Luther GW III (2009) Time-series chemical and temperature habitat characterization of diffuse flow hydrothermal sites at 9°50′N East Pacific Rise. Deep Sea Res II 56:1616–1621CrossRefGoogle Scholar
  38. Mottl MJ, Seewald JS, Wheat CG, Tivey MK, Michael PJ, Proskurowski G, McCollom TM et al (2011) Chemistry of hot springs along the Eastern Lau Spreading Center. Geochim Cosmochim Acta 75(4):1013–1038CrossRefGoogle Scholar
  39. Mullaugh KM, Luther GW III, Ma S, Moore TS, Yücel M, Becker EL, Podowski EL, Fisher CR, Trouwborst RE, Pierson BK (2008) Voltammetric (Micro) electrodes for the in situ study of Fe2+ oxidation kinetics in hot springs and S2O3 2− production at hydrothermal vents. Electroanalysis 20(3):280–290CrossRefGoogle Scholar
  40. Nees HA, Moore TS, Mullaugh KM, Holyoke RR, Janzen CP, Ma S, Metzger E, Waite TJ, Yücel M, Lutz RA, Shank TM, Vetriani C, Nuzzio DB, Luther GW III (2008) Hydrothermal vent mussel habitat chemistry, pre- and post- eruption at 9°50′ north on the East Pacific Rise. J Shellfish Res 27(1):169–175CrossRefGoogle Scholar
  41. O’ Brien DJ, Birkner FB (1977) Kinetics of oxygenation of reduced sulfur species in aqueous solution. Environ Sci Technol 11:1114–1120CrossRefGoogle Scholar
  42. Podowski EL, Moore TS, Zelnio KA, Luther GW III, Fisher CR (2009) Distribution of diffuse flow megafauna in two sites on the Eastern Lau Spreading Center, Tonga. Deep Sea Res I 56:2041–2056CrossRefGoogle Scholar
  43. Podowski EL, Ma S, Luther GW III, Wardrop D, Fisher CR (2010) Biotic and abiotic factors affecting the distributions of megafauna in diffuse flow on andesite and basalt along the Eastern Lau Spreading Center, Tonga. Mar Ecol Prog Ser 418:25–45CrossRefGoogle Scholar
  44. Pyzik AJ, Sommer SE (1981) Sedimentary iron monosulfides: kinetics and mechanism of formation. Geochim Cosmochim Acta 45:687–698CrossRefGoogle Scholar
  45. Rozan TF, Theberge SM, Luther GW III (2000) Quantifying elemental sulfur (S0) bisulfide (HS) and polysulfides (Sx2−) using a voltammetric method. Anal Chim Acta 415:175–184CrossRefGoogle Scholar
  46. Sander SG, Koschinsky A, Massoth GJ, Stott M, Hunter KA (2007) Organic complexation of copper in deep-sea hydrothermal vent systems. Environ Chem 4:81–89CrossRefGoogle Scholar
  47. Sarradin PM, Waeles M, Bernagout S, Le Gall C, Sarazin J, Riso R (2009) Speciation of dissolved copper within an active hydrothermal edifice on the Lucky Strike vent field (MAR, 37oN). Sci Total Environ 407:869–878Google Scholar
  48. Sarrazin J, Juniper SK, Massoth G, Legendre P (1999) Physical and chemical factors influencing species distributions on hydrothermal sulfide edifices of the Juan de Fuca Ridge, northeast Pacific. Mar Ecol Prog Ser 190:89–112CrossRefGoogle Scholar
  49. Scheirer DS, Shank TM, Fornari DJ (2006) Temperature variations at diffuse and focused flow hydrothermal vent sites along the northern East Pacific Rise. Geochem Geophys Geosyst 7:3Google Scholar
  50. Shank TM, Fornari DJ, Von Damm KL, Lilley MD, Haymon RM, Lutz RA (1998) Temporal and spatial patterns of biological community development at nascent deep-sea hydrothermal vents (9050’N East Pacific Rise). DSR II 45:465–515Google Scholar
  51. Stanbury D (1989) Reduction potentials involving inorganic free radicals in aqueous solution. In: Sykes AG (ed) Advances in inorganic chemistry, vol 33. Academic Press, New York, pp 69–138Google Scholar
  52. Stumm W, Morgan JJ (1996) Aquatic chemistry, 3rd edn. Wiley, New YorkGoogle Scholar
  53. Vairavamurthy A, Manowitz B, Luther GW III, Jeon Y (1993) Oxidation state of sulfur in thiosulfate and implications for anaerobic energy metabolism. Geochim Cosmochim Acta 57:1619–1623CrossRefGoogle Scholar
  54. Vazquez FG, Zhang J, Millero FJ (1989) Effect of metals on the rate of the oxidation of H2S in seawater. Geophys Res Lett 16(12):1363–1366CrossRefGoogle Scholar
  55. Vetter RD, Fry B (1998) Sulfur contents and sulfur-isotope compositions of thiotrophic symvioses in bivalve molluscs and vestimentiferan worms. Mar Biol 132:453–460CrossRefGoogle Scholar
  56. Waite TJ, Moore TS, Childress JJ, Hsu-Kim H, Mullaugh KM, Nuzzio DB, Paschal AN, Tasang J, Fisher CR, Luther GW III (2008) Variation in sulfur speciation with shellfish presence at a Lau Basin diffuse flow vent site. J Shellfish Res 27(1):163–168CrossRefGoogle Scholar
  57. Wang F, Tessier A, Buffle J (1998) Voltammetric determination of elemental sulfur in pore waters. Limnol Oceanogr 43(6):1353–1361CrossRefGoogle Scholar
  58. Yao W, Millero FJ (1996) Oxidation of hydrogen sulfide by hydrous Fe(III) oxides in seawater. Mar Chem 52:1–16CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  • Amy Gartman
    • 1
  • Mustafa Yücel
    • 1
    • 7
  • Andrew S. Madison
    • 1
  • David W. Chu
    • 2
  • Shufen Ma
    • 1
    • 6
  • Christopher P. Janzen
    • 3
  • Erin L. Becker
    • 4
  • Roxanne A. Beinart
    • 5
  • Peter R. Girguis
    • 5
  • George W. LutherIII
    • 1
  1. 1.School of Marine Science and Policy, College of Earth, Ocean and EnvironmentUniversity of DelawareLewesUSA
  2. 2.Department of Chemistry and Biochemistry, School of Marine Science and Policy, College of Earth, Ocean and EnvironmentUniversity of DelawareLewesUSA
  3. 3.Department of ChemistrySusquehanna UniversitySelinsgroveUSA
  4. 4.Biology DepartmentPenn State UniversityUniversity ParkUSA
  5. 5.Department of Organismic & Evolutionary BiologyHarvard UniversityCambridgeUSA
  6. 6.Department of Earth and Planetary ScienceUniversity of CaliforniaBerkeleyUSA
  7. 7.Laboratory of Benthic Ecogeochemistry (LECOB), Observatoire Oceanologique de BanyulsUniversité Pierre et Marie Curie—Paris 6Banyuls-sur-merFrance

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